JPH03237467A - Toner for developing electrostatic charge image - Google Patents
Toner for developing electrostatic charge imageInfo
- Publication number
- JPH03237467A JPH03237467A JP2034454A JP3445490A JPH03237467A JP H03237467 A JPH03237467 A JP H03237467A JP 2034454 A JP2034454 A JP 2034454A JP 3445490 A JP3445490 A JP 3445490A JP H03237467 A JPH03237467 A JP H03237467A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- group
- phenylphenol
- charge
- fine powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 45
- 229920005989 resin Polymers 0.000 abstract description 35
- 239000011347 resin Substances 0.000 abstract description 35
- 239000003795 chemical substances by application Substances 0.000 abstract description 31
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 24
- -1 p-phenylphenol aldehyde Chemical class 0.000 abstract description 23
- 239000011230 binding agent Substances 0.000 abstract description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 6
- 125000001424 substituent group Chemical group 0.000 abstract description 4
- 239000007859 condensation product Substances 0.000 abstract 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 64
- 239000000843 powder Substances 0.000 description 63
- 238000000034 method Methods 0.000 description 38
- 238000012360 testing method Methods 0.000 description 32
- 239000000377 silicon dioxide Substances 0.000 description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- 230000007613 environmental effect Effects 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 239000008096 xylene Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 229930040373 Paraformaldehyde Natural products 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 229920002866 paraformaldehyde Polymers 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004898 kneading Methods 0.000 description 9
- 239000000049 pigment Substances 0.000 description 9
- 229910000859 α-Fe Inorganic materials 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 230000006866 deterioration Effects 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229920006249 styrenic copolymer Polymers 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920003146 methacrylic ester copolymer Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- ARUBXNBYMCVENE-UHFFFAOYSA-N 4-(4-bromophenyl)phenol Chemical compound C1=CC(O)=CC=C1C1=CC=C(Br)C=C1 ARUBXNBYMCVENE-UHFFFAOYSA-N 0.000 description 1
- MVHOIHXEJQPTQT-UHFFFAOYSA-N 4-(4-ethylphenyl)phenol Chemical compound C1=CC(CC)=CC=C1C1=CC=C(O)C=C1 MVHOIHXEJQPTQT-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000001692 EU approved anti-caking agent Substances 0.000 description 1
- 241000257465 Echinoidea Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007877 V-601 Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical group [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- KTVHXOHGRUQTPX-UHFFFAOYSA-N [ethenyl(dimethyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(C)C=C KTVHXOHGRUQTPX-UHFFFAOYSA-N 0.000 description 1
- FCCRGBVYSYHQRQ-UHFFFAOYSA-N [ethenyl(dimethyl)silyl]oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)(C)C=C FCCRGBVYSYHQRQ-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- CAURZYXCQQWBJO-UHFFFAOYSA-N bromomethyl-chloro-dimethylsilane Chemical compound C[Si](C)(Cl)CBr CAURZYXCQQWBJO-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KMVZWUQHMJAWSY-UHFFFAOYSA-N chloro-dimethyl-prop-2-enylsilane Chemical compound C[Si](C)(Cl)CC=C KMVZWUQHMJAWSY-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- PZUGJLOCXUNFLM-UHFFFAOYSA-N n-ethenylaniline Chemical compound C=CNC1=CC=CC=C1 PZUGJLOCXUNFLM-UHFFFAOYSA-N 0.000 description 1
- 150000005209 naphthoic acids Chemical class 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 235000014366 other mixer Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002102 polyvinyl toluene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- MXNUCYGENRZCBO-UHFFFAOYSA-M sodium;ethene;2-methylprop-2-enoate Chemical compound [Na+].C=C.CC(=C)C([O-])=O MXNUCYGENRZCBO-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229920003066 styrene-(meth)acrylic acid ester copolymer Polymers 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- CAPIMQICDAJXSB-UHFFFAOYSA-N trichloro(1-chloroethyl)silane Chemical compound CC(Cl)[Si](Cl)(Cl)Cl CAPIMQICDAJXSB-UHFFFAOYSA-N 0.000 description 1
- FLPXNJHYVOVLSD-UHFFFAOYSA-N trichloro(2-chloroethyl)silane Chemical compound ClCC[Si](Cl)(Cl)Cl FLPXNJHYVOVLSD-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- KHOQXNHADJBILQ-UHFFFAOYSA-N trimethyl(sulfanyl)silane Chemical compound C[Si](C)(C)S KHOQXNHADJBILQ-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、電子写真、静電記録のような画像形成方法に
おける静電荷潜像を顕像化するためのトナーに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a toner for visualizing electrostatic latent images in image forming methods such as electrophotography and electrostatic recording.
従来、電子写真法としては米国特許第２，２９７，６９
１号、特公昭４２−２３９１０号公報、および特公昭４
３−２４７４８号公報などに種々の方法が記載されてい
る。Conventionally, as an electrophotographic method, U.S. Patent No. 2,297,69
1, Special Publication No. 42-23910, and Special Publication No. 4
Various methods are described in Japanese Patent No. 3-24748 and the like.
これらの電子写真法等に適用される現像方法としては、
大別して乾式現像法と湿式現像法とがある。前者は、さ
らに二成分系現像剤を用いる方法と一成分系現像剤を用
いる方法に分けられる。The developing methods applied to these electrophotographic methods include:
Broadly speaking, there are dry development methods and wet development methods. The former method is further divided into methods using a two-component developer and methods using a one-component developer.
これら乾式現像法に適用するトナーとしては、従来、天
然あるいは合成樹脂中に染料、顔料を分散させた着色樹
脂微粉体が、使用されている。例えば、ポリスチレンな
どの結着樹脂中に着色剤を分散させたものを１〜３０μ
ｍ程度に微粉砕した粒子がトナーとして用いられる。磁
性トナーとしては、マグネタイトなどの磁性体粒子を含
有させたものが用いられている。また、二成分系現像剤
を用いる方式の場合には、トナーは通常、ガラスピーズ
、鉄粉、フェライト粒子などのキャリア粒子と混合して
用いられる。As toners applied to these dry developing methods, colored resin fine powders in which dyes and pigments are dispersed in natural or synthetic resins have conventionally been used. For example, a coloring agent dispersed in a binder resin such as polystyrene is 1 to 30 μm.
Particles pulverized to about m size are used as toner. As the magnetic toner, one containing magnetic particles such as magnetite is used. Further, in the case of a system using a two-component developer, the toner is usually mixed with carrier particles such as glass beads, iron powder, and ferrite particles.
いずれのトナーも、現像される静電潜像の極性に応じて
、正または負の電荷を有する必要がある。Either toner must have a positive or negative charge depending on the polarity of the electrostatic latent image being developed.
トナーに電荷を保有させるためには、トナーの成分であ
る樹脂の摩擦帯電性を利用することも出来るが、この方
法ではトナーの帯電性が低いので、現像により得られる
画像はカブリやすく、不鮮明なものとなる。そこで、適
切な摩擦帯電性をトナーに付与するために、帯電性を付
与する染料、顔料、さらには電荷制御剤を添加すること
が行なわれている。In order to make the toner hold an electric charge, it is also possible to use the triboelectricity of the resin that is a component of the toner, but since the toner's chargeability is low with this method, the image obtained by development is prone to fogging and is unclear. Become something. Therefore, in order to impart appropriate triboelectric chargeability to the toner, dyes and pigments that impart chargeability, as well as charge control agents are added to the toner.
今日、当該技術分野で知られている電荷制御剤としては
、モノアゾ染料の金属錯塩、サリチル酸、アルキル置換
サリチル酸、ナフトエ酸、グイカルボン酸の金属錯塩、
銅フタロシアニン顔料等が知られている。Charge control agents known in the art today include metal complexes of monoazo dyes, metal complexes of salicylic acid, alkyl-substituted salicylic acids, naphthoic acids, guicarboxylic acids,
Copper phthalocyanine pigments and the like are known.
しかしながら、これらの電荷制御剤のあるものは、スリ
ーブあるいはキャリアを汚染し易いために、それらを用
いたトナーは複写枚数の増加に伴い摩擦帯電量が低下し
、画像濃度の低下を引き起こす傾向がある。また、ある
種の電荷制御剤は、摩擦帯電量が不十分であり、温湿度
の影響を受は易いために、画像濃度の環境変動の原因と
なる。また、ある種の電荷制御剤は、保存安定性が悪く
、長期保存中に摩擦帯電能が低下する。また、ある種の
電荷制御剤は、樹脂に対する分散性が不良であるために
、これを用いたトナーは粒子間の摩擦帯電量が不均一で
カブリ易い。また、ある秤の電荷制御剤は、熱安定性が
悪くトナー製造時の加熱混練過程において分解変質する
ことがある。そのような電荷制御剤を用いたトナーの一
部を再利用し製造されたトナーは、逆帯電性粒子を生成
しやすくかぶりを生じやすい。また、ある種の電荷制御
剤は、有色であり、カラートナーには実質的に使用でき
ない。However, since some of these charge control agents tend to contaminate the sleeve or carrier, toners using them tend to have a reduced amount of triboelectric charge as the number of copies increases, causing a decrease in image density. . Furthermore, some charge control agents have insufficient triboelectric charge and are easily affected by temperature and humidity, which causes environmental fluctuations in image density. Furthermore, some charge control agents have poor storage stability, and their triboelectric charging ability decreases during long-term storage. Furthermore, since some charge control agents have poor dispersibility in resins, toners using these agents tend to have non-uniform triboelectric charges between particles and are prone to fogging. Further, the charge control agent in a certain scale has poor thermal stability and may be decomposed and deteriorated during the heating and kneading process during toner production. A toner produced by reusing a portion of a toner using such a charge control agent tends to generate oppositely charged particles and tends to cause fogging. Additionally, some charge control agents are colored and cannot be used substantially in color toners.
これら全てを満足する電荷制御剤の開発が強く要請され
ているのが現状である。At present, there is a strong demand for the development of a charge control agent that satisfies all of these requirements.
〔課題を解決するための手段および作用〕本発明者らは
、前記目的を達成するため鋭意検討した結果、下記式（
Ｉ）で示される部分構造式を有し、テトラヒドロフラン
に不溶なｐ−フェニルフェノール−アルデヒド縮合物類
が十分な摩擦帯電能を持つと同時に無色或は実質的に無
色であり、トナーに含有せしめた場合に、このトナーは
十分な摩擦帯電量を持ち、かつ、上記問題点を解決する
ことをＱ出し、本発明に到達したものである。[Means and effects for solving the problem] As a result of intensive studies to achieve the above object, the present inventors found that the following formula (
A p-phenylphenol-aldehyde condensate having the partial structural formula represented by I) and insoluble in tetrahydrofuran has sufficient triboelectric charging ability and is colorless or substantially colorless, and is contained in the toner. In this case, this toner has a sufficient amount of triboelectric charge and solves the above problems, and the present invention was achieved.
式（Ｉ）
１式中、Ｒ８は、水素或はメチル基を示し、Ｒ２及びＲ
３は、それぞれ独立に、水素、炭素数１乃至６のアルキ
ル基、ハロゲン、カルボキシル基、ヒドロキシ基、シア
ン基、ニトロ基、ハロゲン化メチル基、トリメチルシリ
ル基、炭素数１乃至８のエステル基、炭素数１乃至８の
アミド基、炭素数１乃至１２のアシル基、炭素数ｌ乃至
８のスルホニル基、炭素数１乃至８のエーテル基を示す
。〕本発明は、上記（Ｉ）で示される部分構造式を有し
、テトラヒドロフランに不溶なｐ−フェニルフェノール
−アルデヒド縮合物類を負帯電性電荷制御剤として含有
するトナーに関する。Formula (I) 1 In the formula, R8 represents hydrogen or a methyl group, and R2 and R
3 each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms, a halogen, a carboxyl group, a hydroxy group, a cyan group, a nitro group, a halogenated methyl group, a trimethylsilyl group, an ester group having 1 to 8 carbon atoms, and a carbon It represents an amide group having 1 to 8 carbon atoms, an acyl group having 1 to 12 carbon atoms, a sulfonyl group having 1 to 8 carbon atoms, and an ether group having 1 to 8 carbon atoms. The present invention relates to a toner having the partial structural formula (I) above and containing a p-phenylphenol-aldehyde condensate insoluble in tetrahydrofuran as a negatively chargeable charge control agent.
フェノール型化合物が電荷制御剤として用いられる例と
しては、特開昭６３−１３８３５５〜１３８３５７号公
報にアミノ基とフェノール基含有の低分子量樹脂が提案
されている。しかしながら、これらの樹脂は正帯電性付
与を目的としてトナー中に含有されており、本発明とは
目的、及び特性が異なるものである。As an example of using a phenol type compound as a charge control agent, a low molecular weight resin containing an amino group and a phenol group is proposed in JP-A-63-138355-138357. However, these resins are contained in the toner for the purpose of imparting positive chargeability, and their purpose and characteristics are different from those of the present invention.
また、特開昭６３−２６０２５３号公報及び特開昭６３
−２６６４６２号公報には、フェノール化合物がトナー
組成物として提案されている。しかしながら、これらの
フェノール化合物１こついて検討したところ、これらの
フェノール化合物それ自身では、負摩擦帯電性が低く電
荷制御剤としては使用する場合には、樹脂その他のトナ
ー材料に制限を受けることが知見された。Also, JP-A-63-260253 and JP-A-63
JP-A-266462 proposes a phenol compound as a toner composition. However, when these phenolic compounds were studied, it was found that these phenolic compounds themselves have low negative triboelectrification properties, and when used as charge control agents, they are limited by resins and other toner materials. It was done.
また、特公昭５８−９４１５号公報及び特開昭６３−２
６０２５３号公報には、フェノール化合物とアルデヒド
、ケトンとの重Ｗｉ含物あるいはフェノール樹脂が、負
電荷を制御するトナー組成物として提案されている。し
かるに、これらの重縮合物或はフェノール樹脂は、２０
０ ’Ｃ以下で融点或は軟化点を有するため、トナーに
含有せしめた場合には負摩擦（１）電性を有するものの
、下記問題点を有する。Also, Japanese Patent Publication No. 58-9415 and Japanese Patent Publication No. 63-2
Japanese Patent No. 60253 proposes a heavy Wi-containing compound of a phenol compound, an aldehyde, a ketone, or a phenol resin as a toner composition for controlling negative charges. However, these polycondensates or phenolic resins
Since it has a melting point or softening point below 0'C, when it is included in a toner, it has negative triboelectricity (1), but it has the following problems.
１、多くのものは負摩擦帯電性が不十分なため、トナー
中に多量に添加しなければならない。1. Many of them have insufficient negative triboelectric charging properties, so they must be added in large amounts to the toner.
２、添加量によりトナーの定着特性を著しく変えてしま
う。2. The fixing characteristics of the toner are significantly changed depending on the amount added.
３、トナー製造過程における加熱混練時に分解変質する
ために、トナー特性が製造条件に大きく依存する。3. Since the toner is decomposed and deteriorated during heating and kneading in the toner production process, the toner properties largely depend on the production conditions.
４、製造時生じた微粉トナーを再利用して製造したトナ
ーは、かぶりを生じ易い。また、これらに示された重縮
合物あるいはフェノール樹脂は溶剤に対して可溶性であ
るという特徴を有している。4. Toner manufactured by reusing fine powder toner produced during manufacturing tends to cause fogging. Furthermore, the polycondensates or phenolic resins shown above are characterized by being soluble in solvents.
本発明のテトラヒドロフランに不溶なｐ−フェニルフェ
ノール−アルデヒド縮合物類の原材料となる単量体、例
えば、ｐ−フェニルフェノールは、それ自身では帯電付
与能力が低い。しかし、本発明者らは、その単量体をア
ルデヒド類との縮合反応こより、溶剤に可溶なｐ−フェ
ニルフェノール樹脂ではなく、テトラヒドロフランに不
溶なｐ−フェニルフェノール−アルデヒド縮合物とする
ことで、高い負摩擦帯電性を有するとともに前記問題点
を解決することを見出した。The monomer that is a raw material for the tetrahydrofuran-insoluble p-phenylphenol-aldehyde condensate of the present invention, such as p-phenylphenol, has a low charge-imparting ability by itself. However, the present inventors have succeeded in converting the monomer into a tetrahydrofuran-insoluble p-phenylphenol-aldehyde condensate instead of a solvent-soluble p-phenylphenol resin through a condensation reaction with aldehydes. It has been found that the above-mentioned problems can be solved while having high negative triboelectric charging properties.
このテトロヒドロフランに不溶なｐ−フェニルフェノー
ル−アルデヒド縮合物の摩擦帯Ｎ景が高い理由は不明で
あるが、可溶なｐ−フェニルフェノール樹脂が単なる鎖
状構造を有しているのに対し、このテトラヒドロフラン
に不溶なｐ−フェニルフェノール−アルデヒド縮合物は
、置換基のフェニル基部分が架橋し、三次元架橋構造を
有しているためには前制御剤として好ましい性質をする
ようになったと推定される。The reason why the friction zone N-shape of this tetrahydrofuran-insoluble p-phenylphenol-aldehyde condensate is high is unknown, but whereas the soluble p-phenylphenol resin has a simple chain structure, This tetrahydrofuran-insoluble p-phenylphenol-aldehyde condensate is said to have favorable properties as a precontrol agent because the phenyl group moiety of the substituent is crosslinked and has a three-dimensional crosslinked structure. Presumed.
式（１）で示される部分構造式を有し、テトラヒドロフ
ランに不溶なｐ−フェニルフェノ−ルーア；レデヒド縮
合物類は、２５０℃以下で融点、或は軟化点を持たず、
かつ変質しにくいところに特徴がある。そのために、一
般の重縮合物やフェノール樹脂と比較し、トナーの定着
特性に影響することつくない。また、加熱混練時におい
ても分解変質することが少ないので、トナーの帯電特性
が製造条件にあまり依存せず、微粉トナーを再利用して
製造したトナーにおいてもかぶりを生じない、という長
所がある。p-phenylphenol-urea, which has a partial structural formula represented by formula (1) and is insoluble in tetrahydrofuran; redehyde condensates have no melting point or softening point at 250 ° C. or lower,
It is also characterized by its resistance to deterioration. Therefore, compared to general polycondensates and phenolic resins, it does not affect the fixing properties of toner. Furthermore, since it is less likely to be decomposed and altered during heating and kneading, the toner's charging characteristics do not depend much on manufacturing conditions, and it has the advantage that fogging does not occur even in toner manufactured by reusing fine powder toner.
また、本発明の式（１）で示される部分構造式を有し、
テトラヒドロフランに不溶なｐ−フェニルフニノールー
アルデヒド縮合物類においては、フェノール骨格上に、
フェニル基を有するところに特徴がある。従来より知ら
れているフェノール樹脂の場合には、電荷制御剤として
は摩擦帯電能が不十分であるのに比べ、本発明の一般式
（Ｉ）で示される部分構造式を有し、テトラヒドロフラ
ンに不溶なｐ−フェニルフェノール−アルデヒド縮合物
類は摩擦帯電能力が高い。これは、フェニル基の電子求
引性によるためと考えられる。さらにフェニル基に電子
求引性基を有するテトラヒドロフランに不溶なｐ−フェ
ニルフェノール−アルデヒド縮合物類のほうが、摩擦帯
電量が高い傾向にある。Furthermore, it has a partial structural formula represented by formula (1) of the present invention,
In p-phenylphinol aldehyde condensates that are insoluble in tetrahydrofuran, on the phenol skeleton,
It is characterized by having a phenyl group. In the case of conventionally known phenolic resins, the triboelectric charging ability is insufficient as a charge control agent. Insoluble p-phenylphenol-aldehyde condensates have high triboelectric charging ability. This is considered to be due to the electron-withdrawing property of the phenyl group. Furthermore, p-phenylphenol-aldehyde condensates which are insoluble in tetrahydrofuran and which have an electron-withdrawing group in the phenyl group tend to have a higher amount of triboelectric charge.
また、結着樹脂に対する分散性が良好化したために、ト
ナー粒子間の摩擦帯電が均一となり逆帯電粒子の生成が
抑制されて、カブリを生じなくなった。さらに、スリー
ブ、キャリア等のトナー担持体汚染を減少させることが
でき、このトナーを高温高湿下、長く保存した場合でも
良好な画質の画像を得ることができた。さらに、画像の
環境に対する依存性も少な（なり、高温高湿条件下ある
いは低温低湿下においても十分な濃度の画像が得られる
。Furthermore, since the dispersibility in the binder resin was improved, the frictional charging between the toner particles became uniform, the generation of oppositely charged particles was suppressed, and fogging did not occur. Furthermore, contamination of toner carriers such as sleeves and carriers could be reduced, and images of good quality could be obtained even when this toner was stored for a long time under high temperature and high humidity conditions. Furthermore, the dependence of the image on the environment is small (so that images with sufficient density can be obtained even under high temperature and high humidity conditions or under low temperature and low humidity conditions).
以上のように本発明の式（Ｉ）で示される部分構造式を
有し、テトラヒドロフランに不溶なｐフェニルフェノー
ル−アルデヒド縮合物類のほうが、摩擦帯電量が高い傾
向にある。As described above, p-phenylphenol-aldehyde condensates having the partial structural formula represented by formula (I) of the present invention and insoluble in tetrahydrofuran tend to have a higher amount of triboelectric charge.
さらに、本発明の式（１）で示される部分構造式を有し
、テトラヒドロフランに不溶なｐ−フェニルフェノール
−アルデヒド縮合物類は、ＩＲスペクトルにおいて、水
酸基の伸縮振動による吸収帯を３１、７０〜３３００
ｃ ｍ ＋の範囲内に持つ。この吸収帯の位置は、水酸
基が比較的強い水素結合を形成していることを示してい
る。この吸収帯がこれより高波数のものは、帯電量が低
い傾向にある。Furthermore, p-phenylphenol-aldehyde condensates having a partial structural formula represented by formula (1) of the present invention and insoluble in tetrahydrofuran have an absorption band of 31, 70 to 70 due to stretching vibrations of hydroxyl groups in an IR spectrum. 3300
It is within the range of c m +. The position of this absorption band indicates that the hydroxyl groups form relatively strong hydrogen bonds. If the absorption band has a higher wave number than this, the amount of charge tends to be low.
ＩＲスペクトルは、フーリエ変換性を用いた測定機によ
りＫ Ｄ ｒ法によって測定する方法が適当である。The IR spectrum is suitably measured by the K Dr method using a measuring device that uses Fourier transform properties.
本発明の式（Ｉ）で示される部分構造式を有し、テトラ
ヒドロフランに不溶なｐ−フェニルフェノール−アルデ
ヒド縮合物類は、高温に熱することにより一部が、式（
Ｉ）で示される部分構造式に相当する分解物に分解する
。この分解物はマススペクトルにより確認でき、式（Ｉ
）で示される部分構造式に相当するフラグメント、或は
その多量化物のフラグメントがマススペクトルにより検
出できる。The p-phenylphenol-aldehyde condensates which have a partial structural formula represented by formula (I) of the present invention and are insoluble in tetrahydrofuran can be partially converted by heating to a high temperature.
It decomposes into decomposition products corresponding to the partial structural formula shown in I). This decomposition product can be confirmed by mass spectroscopy, and has the formula (I
) Fragments corresponding to the partial structural formula or fragments of multimeric products thereof can be detected by mass spectroscopy.
マススペクトルを測定するには、直接導入法が好ましい
。A direct introduction method is preferred for measuring mass spectra.
本発明の式（Ｉ）で示される部分構造式を有し、テトラ
ヒドロフランに不溶なｐ−フェニルフェノール−アルデ
ヒド縮合物類は、相当するフェノール化合物とアルデヒ
ド類により公知の方法を用いて合成することができる。The p-phenylphenol-aldehyde condensates having the partial structural formula represented by formula (I) of the present invention and insoluble in tetrahydrofuran can be synthesized using the corresponding phenol compound and aldehyde using known methods. can.
本発明のテトラヒドロフランに不溶なｐ−フェニルフェ
ノール−アルデヒド縮合物類は、ｐ−フェニルフェノー
ル類とアルデヒドあるいはバラホルムアルデヒドのよう
なアルデヒド等価体とを有機溶剤中、強塩基を触媒とし
て５０〜２００°Ｃに加熱することによって得ることが
できる。また、ｐ−フェニルフェノール類とアルデヒド
類とから上記合成法にしたがって得られた有機溶剤に可
溶な中間生成拘に、置換基を導入し、さらにアルデヒド
類と強塩基触媒とを加え、縮合させることによっても得
ることができる。The p-phenylphenol-aldehyde condensates insoluble in tetrahydrofuran of the present invention are obtained by preparing p-phenylphenols and aldehydes or aldehyde equivalents such as paraformaldehyde in an organic solvent at 50 to 200°C using a strong base as a catalyst. can be obtained by heating. Further, a substituent is introduced into the intermediate product soluble in organic solvents obtained from p-phenylphenols and aldehydes according to the above synthesis method, and further aldehydes and a strong base catalyst are added to condense the compound. It can also be obtained by
例えば、ｐ−フェニルフェノールとバラホルムアルデヒ
ドの１’１２ｊ ＝物の場合には、キシレンを溶剤、水
酸化つりウニを触媒として、ｐ−フェニルフェノールと
過剰のバラホルムアルデヒドとを混合し、６０℃にて６
時間加熱撹拌し、次いで１４０℃にて１０時間加熱撹拌
することによって得ることができる。For example, in the case of 1'12j = p-phenylphenol and paraformaldehyde, p-phenylphenol and excess paraformaldehyde are mixed using xylene as a solvent and hydroxide sea urchin as a catalyst, and the mixture is heated at 60°C. 6
It can be obtained by heating and stirring for an hour and then heating and stirring at 140°C for 10 hours.
また、臭素を置換基に持った縮合物の場合には、ｐ−フ
ェニルフェノールとホルムアルデヒドとをキシレン溶剤
に混合し、水酸化カリウムを触媒として１００°Ｃにて
６時間加熱撹拌することによって可溶性のｐ−フェニル
フェノール縮合物を得、継いでこれにテトラヒドロフラ
ン溶媒中、臭素を反応させ、これをさらにキシレン溶剤
中、水酸化カリウムを触媒としてホルムアルデヒドと１
３０℃で反応させることによって不溶な縮合物を得るこ
とができる。In addition, in the case of a condensate having bromine as a substituent, p-phenylphenol and formaldehyde are mixed in xylene solvent, and the mixture is heated and stirred at 100°C for 6 hours using potassium hydroxide as a catalyst. A p-phenylphenol condensate was obtained, which was then reacted with bromine in a tetrahydrofuran solvent, and further reacted with formaldehyde in a xylene solvent using potassium hydroxide as a catalyst.
An insoluble condensate can be obtained by reacting at 30°C.
以下に本発明に用いうるｐ−フェニルフェノール−アル
デヒド縮合物類の具体例を示すが、これは、取扱の容易
さ等も考慮した代表例であり本発明の化合物を何ら限定
するものではない。Specific examples of p-phenylphenol-aldehyde condensates that can be used in the present invention are shown below, but these are representative examples in consideration of ease of handling, etc., and are not intended to limit the compounds of the present invention in any way.
化合物例
（１）ｐ−フェニルフェノールとバラホルムアルデヒド
とをキシレンを溶剤、水酸化カリウムを触媒として反応
させて得られる縮合物。Compound Example (1) A condensate obtained by reacting p-phenylphenol and paraformaldehyde using xylene as a solvent and potassium hydroxide as a catalyst.
（２）ｐ−（４−ブロモフェニル）フェノールとバラホ
ルムアルデヒドとをキシレンを溶剤、水酸化カリウムを
触媒として反応させて得られる縮合物。(2) A condensate obtained by reacting p-(4-bromophenyl)phenol and paraformaldehyde using xylene as a solvent and potassium hydroxide as a catalyst.
（３）ｐ−フェニルフェノールとホルムアルデヒドとを
キシレン溶剤に混合し、水酸化カリウムを触媒として反
応させて可溶性のｐ−フェニルフェノール縮合物を得、
継いでこれにテトラヒドロフラン溶媒中、臭素を反応さ
せ、さらにこれをキシレン溶剤中、水酸化カリウムを触
媒としてホルムアルデヒドと反応させることによって得
られる縮合物。(3) mixing p-phenylphenol and formaldehyde in xylene solvent and reacting with potassium hydroxide as a catalyst to obtain a soluble p-phenylphenol condensate;
A condensate obtained by subsequently reacting this with bromine in a tetrahydrofuran solvent, and then reacting this with formaldehyde in a xylene solvent using potassium hydroxide as a catalyst.
（４）ビフェニル−４，４′ −ジオールとパラホルム
アルデヒドとをキシレンを溶剤、水酸化カリウムを触媒
として反応させて得られる縮合物。(4) A condensate obtained by reacting biphenyl-4,4'-diol and paraformaldehyde using xylene as a solvent and potassium hydroxide as a catalyst.
（５）ｐ−（４−クロロフェニル）フェノールトハラホ
ルムアルデヒドとをキシレンを溶剤、水酸化カリウムを
触媒として反応させて得られる縮合物。(5) A condensate obtained by reacting p-(4-chlorophenyl)phenoltohaloformaldehyde with xylene as a solvent and potassium hydroxide as a catalyst.
（６） ｐ−（４−エチルフェニル）フェノールとパラ
ホルムアルデヒドとをキシレンを溶剤、水酸化ナトリウ
ムを触媒として反応させて得られる縮合物。(6) A condensate obtained by reacting p-(4-ethylphenyl)phenol and paraformaldehyde using xylene as a solvent and sodium hydroxide as a catalyst.
（７）ｐ−（４トリメチルンリルフエニル）フェノール
とパラホルムアルデヒドとをキシレンを溶剤、水酸化カ
リウムを触媒として反応させて得られる縮合物。(7) A condensate obtained by reacting p-(4trimethylunrylphenyl)phenol and paraformaldehyde using xylene as a solvent and potassium hydroxide as a catalyst.
（８）ｐ−フェニルフェノールとパラホルムアルデヒド
とをキシレンを溶剤、水酸化ナトリウムを触媒として反
応させて得られる縮合物。(8) A condensate obtained by reacting p-phenylphenol and paraformaldehyde using xylene as a solvent and sodium hydroxide as a catalyst.
（９）ｐ−フェニルフェノールとパラホルムアルデヒド
とをキシレンを溶剤、水酸化ルビジウムを触媒として反
応させて得られる縮合物。(9) A condensate obtained by reacting p-phenylphenol and paraformaldehyde using xylene as a solvent and rubidium hydroxide as a catalyst.
本発明においてｐ−フェニルフェノール−アルデヒド縮
合物類をトナーに含有させる方法としては、トナー内部
に添加する方法と外添する方法とがある。これらの化合
物の使用量は、結着樹脂の種類、必要に応じて使用され
る添加剤の有無、分散方法を含めたトナー製造方法によ
って決定されるもので、一義的に限定されるものではな
いが、内添する場合は、好ましくは結着樹脂１００重量
部に対して０．１〜１０重量部、より好ましくは０．１
〜５重量部の範囲で用いられる。また外添する場合は、
樹脂１００重量部に対し０．０１〜１０重量部が好まし
い。In the present invention, methods for incorporating p-phenylphenol-aldehyde condensates into the toner include a method of adding it inside the toner and a method of adding it externally. The amount of these compounds used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner manufacturing method, including the dispersion method, and is not uniquely limited. However, when internally added, preferably 0.1 to 10 parts by weight, more preferably 0.1 parts by weight per 100 parts by weight of the binder resin.
It is used in a range of 5 parts by weight. Also, when adding externally,
It is preferably 0.01 to 10 parts by weight per 100 parts by weight of the resin.
外添する場合は特に、結着樹脂、着色剤よりなる微粒子
の表面近傍に機械的衝撃により固着または埋設させるの
が好ましい。When externally added, it is particularly preferable to fix or embed the binder resin or colorant near the surface of the fine particles by mechanical impact.
先ず、前処理として電荷制御剤（粒子（Ｂ））を分散し
つつ、着色微粒子（粒子（Ａ））と摩擦せしめて静電力
及びファンデルワールス力により着色微粒子に付着せし
める。−船釣には高速の撹拌羽根イ４きの混合機が用い
られるが、混合機能と分散機能を有するものであれば良
い。また、粉砕機、振動ミル等を衝撃力を落として使用
しても良い。この前処理分散をより均一なものにするた
めに、必要に応じて分散補助剤として流動性付与剤、潤
滑材、導電性付与剤などを添加しても良い。First, as a pretreatment, the charge control agent (particles (B)) is dispersed and rubbed against the colored fine particles (particles (A)) so that it adheres to the colored fine particles by electrostatic force and van der Waals force. - A mixer with four high-speed stirring blades is used for boat fishing, but any mixer with mixing and dispersion functions will suffice. Alternatively, a crusher, vibrating mill, etc. may be used with reduced impact force. In order to make this pretreatment dispersion more uniform, a fluidity imparting agent, a lubricant, a conductivity imparting agent, etc. may be added as a dispersion aid, if necessary.
また、本発明のｐ−フェニルフェノール−アルデヒド縮
合物類は、アルキルサリチル酸錯塩、モノアゾ染料の金
属錯塩、ホウ素化合物、スルホン酸ペンダント化樹脂等
の従来公知の電荷制御剤と組み合わせて使用することも
できる。Furthermore, the p-phenylphenol-aldehyde condensates of the present invention can also be used in combination with conventionally known charge control agents such as alkyl salicylic acid complex salts, metal complex salts of monoazo dyes, boron compounds, and sulfonic acid pendant resins. .
また、本発明のトナーにおいては、ドナーにシリつ微粉
体を外添して使用することができる。シＪつ微粉体とし
ては、乾式法及び湿式法で製造したシリカ微粉体が使用
できる。Further, in the toner of the present invention, fine silica powder can be externally added to the donor. As the fine powder, silica fine powder produced by a dry method or a wet method can be used.
ここで言う乾式法とは、ケイ素ハロゲン化合物の蒸気相
酸化により生成するシリカ微粉体の製造法である。例え
ば、四塩化ケイ素ガスの酸素水素中における熱分解酸化
反応を利用する方法で、基礎となる反応式は次の様なも
のである。The dry method mentioned here is a method for producing fine silica powder produced by vapor phase oxidation of a silicon halide compound. For example, this method utilizes a thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen and hydrogen, and the basic reaction formula is as follows.
５ＩＣ１４＋２Ｈ２＋０２→Ｓｉ○２＋４ＨＣ１又、こ
の製造工程において例えば、塩化アルミニウム又は、塩
化チタンなどの他の金属ハロゲン化合物をケイ素ハロゲ
ン化合物と共に用いる事によってシリカと他の金属酸化
物の複合微粉体を得る事も可能であり、それらも包含す
る。5IC14+2H2+02→Si○2+4HC1 Also, in this manufacturing process, it is also possible to obtain a composite fine powder of silica and other metal oxides by using other metal halide compounds such as aluminum chloride or titanium chloride together with a silicon halide compound. and includes them as well.
一方、本発明に用いられるシリカ微粉体を湿式法で製造
する方法は、従来公知である種々の方法が適用できる。On the other hand, various conventionally known methods can be applied to produce the silica fine powder used in the present invention by a wet method.
例えば、ケイ素ナトリウムの酸による分解、一般反応式
で示せば（以下反応式は略す）、
Ｎａ ２ ０ ◆ＸＳｉ○ ２ ＋ ＨＣｌ２ ＋
Ｈ２０＋ＳｉＯ２・ｎＨ２０＋Ｎａ（Ｊ！
その池、ケイ酸ナトリウムのアンモニア塩類又はアルカ
リ塩類による分解、ケイ酸ナトリウムよりアルカリ土類
金属ケイ酸塩を生成せしめた後、酸で分解しケイ酸とす
る方法、ケイ酸ナトリウム溶液をイオン交換樹脂により
ケイ酸とする方法、天然ケイ酸又はケイ酸塩を利用する
方法などがある。For example, the decomposition of sodium silicon by acid is expressed by the general reaction formula (the reaction formula is omitted below): Na 2 0 ◆XSi○ 2 + HCl2 +
H20+SiO2・nH20+Na (J! Sonoike, decomposition of sodium silicate with ammonia salts or alkali salts, method of producing alkaline earth metal silicate from sodium silicate and then decomposing it with acid to produce silicic acid, silicic acid There are methods such as converting a sodium solution into silicic acid using an ion exchange resin, and methods using natural silicic acid or silicate.
ここでいうシリカ微粉体には、無水二酸化ケイ素（ノリ
力）、その他、ケイ酸アルミニウム、ケイ酸ナトリウム
、ケイ酸カリウム、ケイ酸マグネンウム、ケン酸亜鉛な
どのケイ酸塩をいずれも適用できる。As the silica fine powder referred to herein, any of anhydrous silicon dioxide (Noriyaku) and other silicates such as aluminum silicate, sodium silicate, potassium silicate, magnenium silicate, and zinc citrate can be used.
上記シリカ微粉体のうちで、ＢＥＴ法で測定した窒素吸
着による比表面積が３０ ｒｄ ／ ｇ以上（特に５０
〜４００ ｒｄ ／ ｇ ）の範囲内のものが良い。Among the above silica fine powders, the specific surface area due to nitrogen adsorption measured by the BET method is 30 rd/g or more (especially 50 rd/g or more).
~400 rd/g) is preferable.
又、本発明に用いられるシリカ微粉体は、必要に応じて
７ランカツプリング剤、疎水化の目的で有機ケイ素化合
物などの処理剤で処理されていても良く、その方法も公
知の方法が用いられ、シリカ微粉体と反応或は物理吸着
する上記処理剤で処理される。その様な処理剤としては
、例えば、ヘキサメチルジノラザン、トリメチル７ラン
、トリメチルクロルシラン、トリメチルエトキシシラン
、ツメチルジクロルシラン、メチルトリクロルシラン、
アリルジメチルクロルシラン、アリルフエニルジクロル
７ラン、ベンブルジメチルクロルシラン、ブロムメチル
ジメチルクロルシラン、α−クロルエチルトリクロルン
ラン、β−クロルエチルトリクロルシラン、クロルメチ
ルジメチルクロルンラン、トリオルガノシリルメルカプ
タン、トリメチルシリルメルカプタン、トリオルガノシ
リルアクリレート、ビニルジメチルアセトキシシラン、
ジメチルニドキシンラン、ジメチルジメトキンシラン、
ジフェニルジェトキシシラン、ヘキサメチルジ／ロキサ
ン、１．３−’）ビニルテトラメチルジシロキサン、！
、３−ジフェニルテトラメチルジシロキサン、及び１分
子当たり２から１２個のシロキサン単位を有し末端に位
置する単位にそれぞれ１個宛のＳｉに結合した水酸基を
含有するジメチルポリソロキサン等がある。これらは１
種或は２種以上の混合物で用いられる。Further, the silica fine powder used in the present invention may be treated with a treatment agent such as a 7-run coupling agent or an organosilicon compound for the purpose of hydrophobization, if necessary, and a known method may be used. and treated with the above-mentioned treatment agent that reacts with or physically adsorbs the silica fine powder. Examples of such treatment agents include hexamethyldinolazan, trimethyl 7rane, trimethylchlorosilane, trimethylethoxysilane, trimethyldichlorosilane, methyltrichlorosilane,
Allyldimethylchlorosilane, allyl phenyldichlor7lan, bembrodimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorsilane, β-chloroethyltrichlorsilane, chloromethyldimethylchloranran, triorganosilyl mercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane,
Dimethylnidoxinlan, dimethyldimethquinsilane,
Diphenyljethoxysilane, hexamethyldi/loxane, 1.3-') vinyltetramethyldisiloxane,!
, 3-diphenyltetramethyldisiloxane, and dimethylpolysoloxane having 2 to 12 siloxane units per molecule and containing one Si-bonded hydroxyl group in each unit located at the end. These are 1
It is used either as a species or as a mixture of two or more species.
最終的に、処理されたシリカ微粉体の疎水化度がメタノ
ール滴定試験によって測定された疎水化度として、３０
〜８０の範囲の値を示す様に疎水化された場合にこの様
なシリカ微粉体を含有する現像剤の摩擦帯電量がシャー
プで均一なる負荷電性を示す様になるので好ましい。こ
こでメタノール滴定試験では疎水化された表面を有する
シリカ微粉体の疎水化度の程度が確認される。Finally, the degree of hydrophobicity of the treated silica fine powder was determined to be 30 as measured by methanol titration test.
When the developer is hydrophobized so as to exhibit a value in the range of .about.80, the amount of triboelectric charge of the developer containing such fine silica powder becomes sharp and exhibits uniform negative electrification, which is preferable. Here, in the methanol titration test, the degree of hydrophobization of the silica fine powder having a hydrophobized surface is confirmed.
処理されたシリカ微粉体に疎水化度を評価するために本
明細書において規定される″メタノール滴定試験”は次
の如く行なう。供試シリカ微粉体Ｑ、 ２ｇを容量２５
０ ｍ ｌの三角フラスコ中の水５０ｍｊ！に添加する
。メタノールをビューレットからシリカの全量が湿潤さ
れるまで滴定する。この際、フラスコ内の溶液はマグネ
チツクスクーラーで常時撹拌する。その終点はシリカ微
粉体の全量が液体中にせ濁されることによって観察され
、疎水化度は終１点に達した際のメタノール及び水の液
状混合物中のメタノールの百分率として表わされる。The "methanol titration test" specified herein for evaluating the degree of hydrophobicity of the treated silica fine powder is carried out as follows. Sample silica fine powder Q, 2g in a capacity of 25
50mj of water in a 0ml Erlenmeyer flask! Add to. Methanol is titrated from the burette until all of the silica is wetted. At this time, the solution in the flask is constantly stirred using a magnetic cooler. The end point is observed when the entire amount of fine silica powder is suspended in the liquid, and the degree of hydrophobicity is expressed as the percentage of methanol in the liquid mixture of methanol and water when the end point is reached.
本発明に使用される着色剤としては、カーボンブラック
、ランプブラック、鉄黒、群青、ニグロシン染料、アニ
リンブルー、フタロシアニンブルーフタロンアニングリ
ーン、ハンザイエロー６１０−ダミン６Ｇ、カルコオイ
ルブルー、クロムイエローキナクリドン、ベンジジンイ
エロー ローズベンガル、トリアリールメタン系染料、
モノアゾ系、ジスアゾ系染顔料等従来公知の染顔料を単
独或は混合して使用し得る。Coloring agents used in the present invention include carbon black, lamp black, iron black, ultramarine blue, nigrosine dye, aniline blue, phthalocyanine blue phthalone aniline green, Hansa Yellow 610-Damine 6G, calco oil blue, chrome yellow quinacridone, Benzidine Yellow Rose Bengal, triarylmethane dye,
Conventionally known dyes and pigments such as monoazo and disazo dyes and pigments may be used alone or in combination.
本発明に使用される樹脂としては、例えば、ポリスチレ
ン、ポリ−ｐ−クロルスチレン、ポリビニルトルエンな
どのスチレン及びその置換体の単重合体；スチレン−ｐ
〜クロルスチレン共重合体、スチレン−ビニルトルエン
共重合体、スチレン−ビニルナフタリン共重合体、スチ
レン−アクリル酸エステル共重合体、スチレン−メタク
リル酸エステル共重合体、スチレン−α−クロルメタク
リル酸メチル共重合体、スチレン−アクリロニトリル共
重合体、スチレン−ビニルメチルエーテル共重合体、ス
チレン−ビニルエチルエーテル共重合体、スチレン−ビ
ニルメチルケトン共重合体、スチレン−ブタジェン共重
合体、スチレン−イソプレン共重合体、スチレン−アク
リロニトリル−インデン共重合体などのスチレン系共重
合体・ポリ塩化ビニル、フェノール樹脂、天然変性フェ
ノール樹脂、天然樹脂変性マレイン酸樹脂、アクリル樹
脂、メタクリル樹脂、ポリ酢酸ビニール、シリコーン樹
脂、ポリエステル樹脂、ポリウレタン、ポリアミド樹脂
、フラン樹脂、エポキシ樹脂、キシレン樹脂、ポリビニ
ルブチラール、テルペン樹脂、クマロインデン樹脂、石
油系樹脂などが使用できる。Examples of the resin used in the present invention include monopolymers of styrene and substituted products thereof such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene;
~Chlorstyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-methyl chloromethacrylate copolymer Polymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer , styrenic copolymers such as styrene-acrylonitrile-indene copolymer, polyvinyl chloride, phenolic resin, naturally modified phenolic resin, natural resin-modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester Resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaroindene resin, petroleum resin, etc. can be used.
また、架橋されたスチレン系共重合体も好ましい結着樹
脂である。Further, crosslinked styrenic copolymers are also preferred binder resins.
スチレン系共重合体のスチレンモノマーに対するコモノ
マーとしては、例えば、アクリル酸、アクリル酸メチル
、アクリル酸エチル、アクリル酸ブチル、アクリル酸ド
デシル、アクリル酸オクチル、アクリル酸−２−エチル
ヘキシル、アクリル酸フェニル、メタクリル酸、メタク
リル酸メチル、メタクリル酸エチル、メタクリル酸ブチ
ル、メタクリル酸オクチル、アクリロニトリル、メタク
リロニトリル、アクリルアミドなどの様な二重結合をＴ
Ｔするモノカルボン酸もしくはその置換体；例えば、マ
レイン酸、マレイン酸ブチル、マレイン酸酸メチル、マ
レイン酸ジメチルなどの様な二重結合を有するジカルホ
ン酸及びその置換体；例えば塩化ビニル、酢酸ビニル、
安息香酸ビニルなどの様なビニルエステル類；例えばエ
チレン、プロピレン、ブチレンなどの様なエチレン系オ
レフィン類；例えばビニルメチルケトン、ビニルメチル
ケトンなどの様なビニルケトン類１例えばビニルメチル
エーテル、ビニルエチルエーテル、ビニルイソブチルエ
ーテルなどの様なビニルエーテル類；等のビニル単量体
が単独もしくは２つ以上用いられる。Examples of comonomers for the styrene monomer in the styrenic copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, and methacrylate. acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc.
T monocarboxylic acids or substituted products thereof; for example, dicarphonic acids having double bonds such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate, etc.; and substituted products thereof; for example, vinyl chloride, vinyl acetate,
Vinyl esters such as vinyl benzoate; ethylene olefins such as ethylene, propylene, butylene; vinyl ketones 1 such as vinyl methyl ketone, vinyl methyl ketone, etc. Vinyl monomers such as vinyl ethers such as vinyl isobutyl ether may be used alone or in combination of two or more.
ここで架橋剤としては、主として２個以上の重合可能な
二重結合を有する化合物が用いられ、例えば、ジビニル
ベンゼン、ジビニルナフタレンなどの様な芳香族ジビニ
ル化合物；例えばエチレングリコールンアクリレート、
エチレングリコールジメタクリレート、１． ３−ブタ
ンジオールジメタクリレートなどの様な二重結合を２個
有するカルボン酸エステル；ンビニルアニリン、ジビニ
ルエーテル、ジビニルスルフィド、ジビニルスルホンな
どのジビニル化合物；及び３個以上のビニル基を有する
化合物；が単独もしくは混合物として用いられる。As the crosslinking agent, compounds having two or more polymerizable double bonds are mainly used, such as aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; for example, ethylene glycol acrylate,
Ethylene glycol dimethacrylate, 1. Carboxylic acid esters having two double bonds such as 3-butanediol dimethacrylate; divinyl compounds such as vinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups; Used alone or in mixtures.
また、加圧定着方式を用いる場合には、圧力定着トナー
用結着樹脂の使用が可能であり、例えばポリエチレン、
ポリプロピレン、ポリメチレン、ポリウレタンエラスト
マー、エチレン−エチルアク、；レート共重合体、エチ
レン−酢酸ビニル共重合体、アイオノ７−樹脂、スチレ
ン−ブタジェン共重合体、スチレン−イソプレン共重合
体、線状能＋ｌ］ポリエ只チル、パラフィンなどがある
。In addition, when using a pressure fixing method, it is possible to use a binder resin for pressure fixing toner, such as polyethylene,
Polypropylene, polymethylene, polyurethane elastomer, ethylene-ethyl acetate, ;rate copolymer, ethylene-vinyl acetate copolymer, iono-7-resin, styrene-butadiene copolymer, styrene-isoprene copolymer, linear performance +l] polyester There are simple chills, paraffin, etc.
また、本発明の静電荷現像用トナーは磁性材料を含有さ
せて磁性トナーとして用いることも出来る。田いられる
磁性材料としては、マグネタイト、γ−酸化鉄、フェラ
イト、鉄過剰型フェライト等の酸化鉄；訣、コバルト、
ニッケルなどの金属或はこれらの金属とアルミニウム、
コバルト、銅、鉛、マグネシウム、スズ、亜鉛、アンチ
モン、ベリリウム、ビスマス、カドミウム、カルシウム
、マンガン、セレン、チタン、タングステン、バナジウ
ムの様な金属との合金およびその混合物等が挙げられる
。これらの磁性材料は平均粒型が０．１〜１μｍ、好ま
しくは０．１〜０．５μｍ程度のものが望ましく、磁性
トナー中に含有させる量としては結着樹脂成分１００重
量部に対して４０〜１５０重量部、好ましくは６０〜１
２０重量部である。Further, the toner for electrostatic charge development of the present invention can also be used as a magnetic toner by containing a magnetic material. Magnetic materials that can be used include iron oxides such as magnetite, γ-iron oxide, ferrite, and iron-rich ferrite; cobalt;
Metals such as nickel or these metals and aluminum,
Examples include alloys with metals such as cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof. It is desirable that these magnetic materials have an average particle size of about 0.1 to 1 μm, preferably about 0.1 to 0.5 μm, and the amount contained in the magnetic toner is 40 parts by weight per 100 parts by weight of the binder resin component. ~150 parts by weight, preferably 60-1
It is 20 parts by weight.
本発明の電荷制御剤を用いた磁性トナーにおいては、体
積平均粒径が３〜１５μｍのトナーが使用可能である、
特に５μｍ以下の粒径を有する磁性トナー粒子が１２〜
６０個数％含有され、８〜１２．７μｍの粒径を有する
磁性トナー粒子が１〜３３個数％含有され、１６μｍ以
上の粒径を有する磁性トナー粒子が２．０体積％以下含
有され、磁性トナーの体積平均粒径が４〜１０μｍであ
ることが現像特性の上からより好ましい。In the magnetic toner using the charge control agent of the present invention, a toner having a volume average particle diameter of 3 to 15 μm can be used.
In particular, magnetic toner particles having a particle size of 5 μm or less
The magnetic toner contains 60% by number, 1 to 33% by number of magnetic toner particles having a particle size of 8 to 12.7 μm, and 2.0% by volume or less of magnetic toner particles having a particle size of 16 μm or more. It is more preferable from the viewpoint of development characteristics that the volume average particle diameter of the toner is 4 to 10 μm.
トナーの粒度分布は種々の方法によって測定できるが、
本発明においてはコールタ−カウンターを用いて行なう
のが適当である。The particle size distribution of toner can be measured by various methods.
In the present invention, it is appropriate to use a Coulter counter.
すなわち、測定装置としてはコールタ−カウンターＴＡ
−ｎ型（コールタ−社製）を用い、個数分布、体積分布
を出力するインターフェイス（日科機製）及びＣＸ−１
パーソナルコンピユータ（キャノン製）を接続し、電解
液は、１級塩化ナトリウムを用いて約１％ＮａＣ１水溶
液を調整する。例えば、ｌ５ＯＴＯＮ■−■（コールタ
−サイエンティフィックジャパン社製）が使用できる。In other words, the measuring device is Coulter counter TA.
- An interface (manufactured by Nikkaki) that outputs the number distribution and volume distribution using the n-type (manufactured by Coulter) and CX-1
A personal computer (manufactured by Canon) is connected, and an approximately 1% NaCl aqueous solution is prepared as an electrolytic solution using primary sodium chloride. For example, 15OTON■-■ (manufactured by Coulter Scientific Japan) can be used.
測定法としては前記電解水溶液１００〜１５０ｍｆ中に
分散剤として界面活性剤、好ましくはアルキルベンゼン
スルホン酸塩を０．１〜５ｍｌ加え、更に測定試料を２
〜２０ｍｇ加える。試料を懸濁した電解液は、超音波分
散器で約１〜３分間分散処理を行ない、前記コールタ−
カウンターＴＡ−Ｉｔ型により、アパチャーとして１０
０μｍアパーチャーを用いて、個数を基準として２〜４
０μｍの粒子の粒度分布を測定、換算して、トナーの粒
度分布を求める。The measurement method is to add 0.1 to 5 ml of a surfactant as a dispersant, preferably an alkylbenzene sulfonate, to 100 to 150 mf of the electrolytic aqueous solution, and then add 2 ml of the measurement sample.
Add ~20 mg. The electrolyte in which the sample was suspended is dispersed in an ultrasonic disperser for about 1 to 3 minutes, and then
With the counter TA-It type, the aperture is 10
Using a 0 μm aperture, 2 to 4 pieces based on the number
The particle size distribution of 0 μm particles is measured and converted to determine the particle size distribution of the toner.
さらに本発明のトナーは、キャリアと混合して二成分ｌ
・ナーとして用いることもできる。本発明に使用し得る
キャリアとしては、公知のものが使用可能であり、例え
ば鉄粉、フェライト粉、ニッケル粉の様な磁性を有する
粉体、ガラスピーズ等、及びこれらの表面を樹脂等で処
理したものが掲げられる。又、キャリア表面を被覆する
樹脂としては、スチレン−アクリル酸エステル共重合体
、スチレン−メタクリル酸エステル共重合体、アクリル
酸エステル共重合体、メタクリル酸エステル共重合体、
シリコーン樹脂、フッ素含有樹脂、ポリアミド樹脂、ア
イオノマー樹脂、ポリフェニレンサルファイド樹脂など
或は、これらの混合物を用いることができる。Further, the toner of the present invention can be mixed with a carrier to form a two-component l
・Can also be used as a ner. As the carrier that can be used in the present invention, known carriers can be used, such as iron powder, ferrite powder, magnetic powder such as nickel powder, glass beads, etc., and carriers whose surfaces are treated with resin etc. Those who have done so will be listed. Further, as the resin for coating the carrier surface, styrene-acrylic ester copolymer, styrene-methacrylic ester copolymer, acrylic ester copolymer, methacrylic ester copolymer,
Silicone resins, fluorine-containing resins, polyamide resins, ionomer resins, polyphenylene sulfide resins, etc., or mixtures thereof can be used.
本発明のトナーは、必要に応じて添加剤を混合してもよ
い。添加剤としては、例えばステアリン酸亜鉛の如き滑
剤、或は酸化セリウム、炭化ケイ素の如き研磨剤或は例
えば酸化アルミニウムの如き流動性付与剤、ケーキング
防止剤、或は例えばカーボンブラック、酸化スズ等の導
電性付与剤がある。The toner of the present invention may contain additives, if necessary. Additives include lubricants such as zinc stearate, abrasives such as cerium oxide and silicon carbide, flow agents such as aluminum oxide, anti-caking agents, or carbon black, tin oxide, etc. There are conductivity imparting agents.
また、ポリビニリデンフルオライド微粉末などの弗素含
有重合体微粉末も流動性、研磨性、帯電安定性などの点
から好ましい添加剤である。Further, fine powder of a fluorine-containing polymer such as fine powder of polyvinylidene fluoride is also a preferable additive from the viewpoint of fluidity, polishability, charging stability, and the like.
また、熱ロール定着時の離型性を良くする目的で低分子
量ポリエチレン、低分子量ポリプロピレン、マイクロク
リスタリンワックス、カルナバワックス、サゾールワッ
クス、パラフィンワックス等のワックス状物質を０．５
〜５重量％程度トナーに加えることも本発明の好ましい
形態の一つである。In addition, in order to improve mold releasability during hot roll fixing, waxy substances such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, carnauba wax, Sasol wax, paraffin wax, etc.
It is also one of the preferred embodiments of the present invention to add about 5% by weight to the toner.
本発明に係るトナーを製造するにあったでは、上述した
様なトナー構成材料をボールミルその他の混合機により
充分混合した後、熱ロールニーダ−エクストルーダーの
熱混練機を用いて良く混練し、冷却固化後、機械的な粉
砕、分級によってトナーを得る方法が好ましい。他には
、結着樹脂溶液中に構成材料を分散した後、噴霧乾燥す
ることによりトナーを得る方法；或いはコア材、シェル
材から成るいわゆるマイクロカプセルトナーにおいて、
コア材或いはノニル材、或いはこれらの両方に所定の材
料を含有させる方法；等の方法が応用できる。In manufacturing the toner according to the present invention, the toner constituent materials as described above are thoroughly mixed using a ball mill or other mixer, then thoroughly kneaded using a heat kneader such as a hot roll kneader-extruder, and then cooled and solidified. After that, it is preferable to obtain the toner by mechanical crushing and classification. Another method is to obtain a toner by dispersing constituent materials in a binder resin solution and then spray drying; or in a so-called microcapsule toner consisting of a core material and a shell material.
Methods such as a method of containing a predetermined material in the core material, nonyl material, or both can be applied.
さらに、結着樹脂を構成すべき単量体に所定材料を混合
して乳化懸濁液とした後に重合させてトナーを得る重合
法トナー製造法を応用できる。Furthermore, it is possible to apply a polymerization toner production method in which a monomer to constitute a binder resin is mixed with a predetermined material to form an emulsified suspension and then polymerized to obtain a toner.
さらに必要に応じ所望の添加剤をヘンシェルミキサー等
の混合機により充分に混合し、本発明に係るトナーを製
造することができる。Furthermore, the toner according to the present invention can be produced by sufficiently mixing desired additives with a mixer such as a Henschel mixer, if necessary.
本発明のトナーは、従来公知の手段で、電子写真、静電
記録及び静電印刷等における静電荷像を顕像化する為の
現像には全て使用可能なものである。The toner of the present invention can be used in all conventionally known methods for developing electrostatic charge images in electrophotography, electrostatic recording, electrostatic printing, and the like.
本発明のｐ−フェニルフェノール−アルデヒド縮合物類
は、無色或は淡色であり、良好な摩擦帯電性を有する。The p-phenylphenol-aldehyde condensates of the present invention are colorless or light-colored and have good triboelectric charging properties.
そのため、本発明のトナーは、連続複写による画質劣化
を起こし難く、しかも濃度均一性の優れた画像を提供し
得る。Therefore, the toner of the present invention is less likely to cause image quality deterioration due to continuous copying and can provide images with excellent density uniformity.
以下、本発明を実施例により具体的に説明するが、これ
は本発明を何ら限定するものではない。尚、以下の配合
における部数は全てｆｆｌｆｆｉ部である。EXAMPLES Hereinafter, the present invention will be specifically explained using Examples, but these are not intended to limit the present invention in any way. Note that all parts in the following formulations are fffffi parts.
実施例１
上記材料をブレンダーでよく混合した後、１５０℃に設
定した２軸混練押出機にて混練した。得られた混練物を
冷却し、カッターミルにて粗粉砕した後、ジェット気流
を用いた微粉砕機を用いて微粉砕し、得られた微粉砕粉
を固定壁型風力分級機で分級した。Example 1 The above materials were thoroughly mixed in a blender and then kneaded in a twin-screw kneading extruder set at 150°C. The obtained kneaded product was cooled and coarsely pulverized using a cutter mill, then finely pulverized using a pulverizer using a jet stream, and the obtained pulverized powder was classified using a fixed wall type wind classifier.
さらに、得られた分級粉をコアンダ効果を利用した多分
割分級装置（日鉄鉱業社製エルボジェット分級機）で超
微粉を同時に厳密に分級除去して体積平均粒径８．５μ
ｍの微粉体を得た。この過程で分級除去されたものを微
粉体Ａとする。Furthermore, the obtained classified powder was thoroughly classified and removed at the same time using a multi-division classification device (Elbowjet classifier manufactured by Nippon Steel Mining Co., Ltd.) that utilizes the Coanda effect, and the volume average particle size was 8.5 μm.
A fine powder of m was obtained. The powder classified and removed in this process is referred to as fine powder A.
得られた微粉体１００部にヘキサメチルジシラザンによ
り疎水化処理したシリカ微粉末（ＢＥＴ比表面積３００
ｒｄ／ｇ）０．６部を加え、ヘンシェルミキサーで混合
してシリカ微粉末を外添されているトナーとした。100 parts of the obtained fine powder was added with silica fine powder (BET specific surface area: 300
rd/g) was added and mixed in a Henschel mixer to obtain a toner to which fine silica powder was externally added.
次いで平均粒径６５μｍのアクリルコートフェライトキ
ャリア１００部に対して得られたトナー５．５部を混合
して現像剤とした。Next, 5.5 parts of the obtained toner was mixed with 100 parts of an acrylic coated ferrite carrier having an average particle size of 65 μm to prepare a developer.
この現像剤を市販のカラー電子写真複写機ＣＬＣ−１（
キャノン（株）製）で複写試験した。This developer was applied to a commercially available color electrophotographic copying machine CLC-1 (
A copying test was conducted using Canon Co., Ltd.).
その結果、２３℃／６０％の環境条件下で、初期から画
像濃度１．４４の鮮やかな黒色画像が得られ、１万枚複
写後の劣化は認められなかった。As a result, under the environmental conditions of 23° C./60%, a bright black image with an image density of 1.44 was obtained from the initial stage, and no deterioration was observed after 10,000 copies were made.
次に、１５°Ｃ／１０％の環境条件下で複写試験したと
ころ、初期から１５４３の高濃度の画像が得られた。Next, when a copying test was conducted under environmental conditions of 15°C/10%, a high density image of 1543 was obtained from the initial stage.
更に、３２°Ｃ／８５％の環境条件下においても、濃度
１．４６の良好な画像が得られた。Furthermore, good images with a density of 1.46 were obtained even under the environmental conditions of 32°C/85%.
実施例２
実施例１におけるカーボンブラック５部を銅フタロシア
ニン顔料（Ｃ，１，ピグメントブルー１５）４部に変え
る以外は実施例１と同様に体積平均粒径８゜１μｍの微
粉体を得、さらにシリカを混合してトナーを得た。Example 2 A fine powder with a volume average particle diameter of 8° and 1 μm was obtained in the same manner as in Example 1, except that 5 parts of carbon black in Example 1 was replaced with 4 parts of copper phthalocyanine pigment (C, 1, Pigment Blue 15), and A toner was obtained by mixing silica.
次いで、実施例１と同じキャリアを同一比率で混合し、
現像剤とした。Next, the same carrier as in Example 1 was mixed in the same ratio,
It was used as a developer.
この現像剤を実施例１と同じ方法で複写試験を行なった
。その結果、２３°Ｃ／６０％の環境条件下で、初期か
ら、濃度１．４３のカブリのない良好な青色画像が得ら
れた。１万枚複写後も画質の劣化は認められなかった。This developer was subjected to a copying test in the same manner as in Example 1. As a result, under the environmental conditions of 23° C./60%, a good blue image with a density of 1.43 and no fog was obtained from the beginning. No deterioration in image quality was observed even after copying 10,000 copies.
また、３５°Ｃ／８５％および１５°Ｃ／１０％の環境
条件下で複写試験を行なったが、２３°Ｃ／６０％の場
合と同様に良好な結果が得られた。Copying tests were also conducted under environmental conditions of 35°C/85% and 15°C/10%, and good results were obtained as in the case of 23°C/60%.
実施例３
実施例１におけるカーンブラック５部をキナクリドン系
顔料（Ｃ，１，ピグメントレッド１２２）４部に変える
以外は実施例１と同様に体積平均粒径８．０μｍの微粉
体を得、さらにシリカを混合してトナーを得た。Example 3 A fine powder with a volume average particle diameter of 8.0 μm was obtained in the same manner as in Example 1 except that 5 parts of Carne Black in Example 1 was changed to 4 parts of a quinacridone pigment (C, 1, Pigment Red 122), and A toner was obtained by mixing silica.
次いで、実施例１と同じキャリアを同一比率で混合し、
現像剤とした。Next, the same carrier as in Example 1 was mixed in the same ratio,
It was used as a developer.
この現像剤を実施例１と同じ方法で複写試験を行なった
。その結果、２３°Ｃ／６０％の環境条件下で、初期か
ら、濃度１．４５のカブリのない良好なマゼンタ画像が
得られた。１万枚複写後も画質の劣化は認められなかっ
た。This developer was subjected to a copying test in the same manner as in Example 1. As a result, under environmental conditions of 23° C./60%, a good magenta image with a density of 1.45 and no fog was obtained from the beginning. No deterioration in image quality was observed even after copying 10,000 copies.
また、３５℃７８５％および１５℃／１０％の環境条件
下で複写試験を行なったが、２３℃／６０％の場合と同
様に良好な結果が得られた。Copying tests were also conducted under environmental conditions of 35°C/785% and 15°C/10%, and similar good results were obtained as in the case of 23°C/60%.
実施例４
実施例１におけるカーボンブラック５部を黄色顔料（Ｃ
，１，ピグメントイエロー１７）５部に変える以外は実
施例１と同様に体積平均粒径８．０μｍの微粉体を得、
さらにシリカを混合してトナーを得た。Example 4 5 parts of carbon black in Example 1 was mixed with yellow pigment (C
, 1, Pigment Yellow 17) A fine powder with a volume average particle size of 8.0 μm was obtained in the same manner as in Example 1 except that the amount was changed to 5 parts.
Furthermore, silica was mixed to obtain a toner.
次いで、実施例１と同じキャリアをキャリア１００部に
対しトナー６部の比率で混合し、現像剤とした。Next, the same carrier as in Example 1 was mixed at a ratio of 100 parts of carrier to 6 parts of toner to prepare a developer.
この現像剤を実施例１と同じ方法で複写試験を行なった
。その結果、２３℃／６０％の環境条件下で、初期から
、濃度１．４４のカブリのない良好な黄色画像が得られ
た。ｌ方杖複写後も画質の劣化は認められなかった。This developer was subjected to a copying test in the same manner as in Example 1. As a result, under environmental conditions of 23° C./60%, a good yellow image with a density of 1.44 and no fog was obtained from the beginning. No deterioration in image quality was observed even after copying.
また、３５ ’Ｃ／ ８５％および１５°Ｃ／１０％の
環境条件下で複写試験を行なったが、２３℃７６０％の
場合と同様に良好な結果が得られた。Copying tests were also conducted under the environmental conditions of 35'C/85% and 15°C/10%, and similar good results were obtained as in the case of 23°C/760%.
実施例５
実施例１〜４で用いたブラック、シアン、マゼンタ、イ
エローの現像剤を用いて、フルカラー画像を得た所、混
色性、階調性に優れた鮮やかなフルカラー画像が得られ
た。Example 5 A full-color image was obtained using the black, cyan, magenta, and yellow developers used in Examples 1 to 4, and a bright full-color image with excellent color mixing and gradation was obtained.
実施例６
上記材料を実施例１と同様にして体積平均粒径８．３μ
ｍの微粉体を得、さらに同じシリカを実施例１と同量混
合してトナーを得た。Example 6 The above material was prepared in the same manner as in Example 1, and the volume average particle diameter was 8.3μ.
A fine powder of m was obtained, and the same amount of silica as in Example 1 was further mixed to obtain a toner.
次いで同じように平均粒径６５μｍのアクリルコートフ
ェライトキャリア１００部に対して得られたトナー５．
５部を混合して現像剤とし、実施例１と同様な評価を行
なった。Next, 5.5 parts of the toner obtained in the same manner was added to 100 parts of an acrylic coated ferrite carrier having an average particle size of 65 μm.
5 parts were mixed to prepare a developer, and the same evaluation as in Example 1 was conducted.
その結果、各環境条件下で、初期から鮮明で高濃度の画
像が得られ、さらに１万枚の複写試験においても良好な
画質の画像が得られた。As a result, under each environmental condition, clear and high-density images were obtained from the beginning, and even in a 10,000 copy test, images of good quality were obtained.
比較例１
実施例１における化合物例（１）２．５部を油溶性ｐ−
フェニルフェノール樹脂（群衆化学工業（株）製、ｐｐ
−８１１）７部に変える以外は、実施例１と同様な方法
により体積平均粒径８，３μｍの微粉体を得、さらに同
じシリカを同比率で混合し、トナーを得た。この過程で
分級除去されたものを微粉体Ｂとする。Comparative Example 1 2.5 parts of Compound Example (1) in Example 1 was added to oil-soluble p-
Phenylphenol resin (manufactured by Crowd Chemical Industry Co., Ltd., pp
-811) A fine powder having a volume average particle diameter of 8.3 μm was obtained in the same manner as in Example 1 except that the amount was changed to 7 parts, and the same silica was further mixed in the same ratio to obtain a toner. The powder classified and removed in this process is referred to as fine powder B.
次に、この微粉体Ｂを実施例６と同じ様にトナー原材料
として再利用し、実施例６における化合物例（１）２．
５部、微粉体Ａ２０部を油溶性ｐ−フェニルフェノール
樹脂７部、微粉体８２０部に変える以外は実施例６と同
様にして体積平均粒径８．７μｍの微粉体を得、さらに
同じシリカを同量混合してトナーを得た。Next, this fine powder B was reused as a toner raw material in the same manner as in Example 6, and compound example (1) 2.
A fine powder with a volume average particle size of 8.7 μm was obtained in the same manner as in Example 6, except that 5 parts of fine powder A and 20 parts of fine powder A were changed to 7 parts of oil-soluble p-phenylphenol resin and 820 parts of fine powder, and the same silica was added. A toner was obtained by mixing the same amounts.
次いで平均粒径６５μｍのアクリルコートフェライトキ
ャリア１００部に対して得られたトナー５部を混合して
現像剤とし、実施例１と同様な評価を行なった。Next, 5 parts of the obtained toner was mixed with 100 parts of acrylic coated ferrite carrier having an average particle size of 65 μm to prepare a developer, and the same evaluation as in Example 1 was conducted.
その結果、２３℃／６０％の環境条件下で、初期には、
画像濃度１．４０の十分な濃度の画像が得られたが、複
写試験を続けるに従い、画像にかぶりを生じるようにな
った。５０００枚複写後においては、このかぶりはひど
くなり、実用上問題となる品質であった。As a result, under the environmental conditions of 23℃/60%, initially,
Although an image with a sufficient density of 1.40 was obtained, as the copying test continued, fogging began to appear in the image. After copying 5,000 sheets, this fog became so severe that the quality became a problem for practical use.
実施例７
上記材料をブレンダーでよく混合した後、１４０℃に設
定した２紬混練押出機にて混練した。得られた混線物を
冷却し、カッターミルにて粗粉砕した後、ジェット気流
を用いた微粉砕機を用いて微粉砕し、得られた微粉砕粉
を固定壁型風力分級機で分級した。Example 7 The above materials were thoroughly mixed in a blender, and then kneaded in a 2-tsumugi kneading extruder set at 140°C. The obtained mixed material was cooled and coarsely pulverized using a cutter mill, then finely pulverized using a pulverizer using a jet stream, and the obtained pulverized powder was classified using a fixed wall type wind classifier.
さらに、得られた分級物をコアンダ効果を利用した多分
割分級装置（０鉄鉱業社製エルボジェット分級機）で超
微粉を同時に厳密に分級除去して体積平均粒径８．６μ
ｍの微粉体を得た。Furthermore, the obtained classified product was subjected to strict classification and removal of ultrafine powder at the same time using a multi-division classifier (elbow jet classifier manufactured by 0 Tetsu Mining Co., Ltd.) that utilized the Coanda effect, and the volume average particle size was 8.6 μm.
A fine powder of m was obtained.
得られた微粉体１００部にヘキサメシルジシラザンによ
り疎水化処理したシリカ微粉末（ＢＥＴ比表面積３００
ｒｒ？／ｇ）０．６部を加え、ヘンシェルミキサーで
混合して磁性トナーとした。100 parts of the obtained fine powder was treated with silica fine powder (BET specific surface area: 300
rr? /g) was added and mixed using a Henschel mixer to obtain a magnetic toner.
このトナーを市販の複写機（商品名ＮＰ−６６５０゜キ
ャノン（株）製）に適用して２３°Ｃ／６０％の環境条
件下、複写試験をしたところ、画像濃度１，３４、カブ
リやがさつきがなく、解像性が６．３本／ ｍ ｍの鮮
明な画像が得られた。さらに、３万枚連続複写して耐久
性能を調べたところ、画像濃度１．３２、解像性６．３
本／ ｍ ｍと初期の画像と比較して遜色のない良好な
画像が得られた。また、現像スリーブ上のトナーの摩擦
帯電量を測定したところ、初期においては−１１，２μ
ｃ／ｇ＋ ３万枚複写後は、ｌ０１７μｃ／ｇで、は
とんどスリーブ汚染は認められなかった。When this toner was applied to a commercially available copying machine (product name NP-6650, manufactured by Canon Co., Ltd.) and subjected to a copying test under environmental conditions of 23°C/60%, the image density was 1.34, and fog and fog were not observed. A clear image with a resolution of 6.3 lines/mm was obtained without any scratches. Furthermore, when we checked the durability performance by continuously copying 30,000 sheets, we found that the image density was 1.32 and the resolution was 6.3.
A good image comparable to that of the original image was obtained. In addition, when we measured the amount of triboelectric charge of the toner on the developing sleeve, we found that it was -11.2μ at the initial stage.
c/g+ After copying 30,000 copies, it was 1017 μc/g, and no sleeve contamination was observed.
次いで、１５°Ｃ／ｌＯ％の環境条件下、複写試験をし
たところ、同様に高濃度で良好な画質の画像が得られた
。３万枚の連続複写試験においても同様に良好な成績で
あった。Next, a copying test was carried out under an environmental condition of 15°C/1O%, and similarly high density and good quality images were obtained. Similarly, good results were obtained in a continuous copying test of 30,000 sheets.
３５°Ｃ／８５％の環境条件下、同じ複写試験、連続複
写試験を行なったところ、良好な結果であった。When the same copying test and continuous copying test were conducted under the environmental conditions of 35°C/85%, good results were obtained.
更にこの環境条件下、このトナーを１か月間放置した後
に同じ複写試験、連続複写試験を行なったが、問題のな
い十分な結果であった。Furthermore, after allowing this toner to stand for one month under these environmental conditions, the same copying test and continuous copying test were conducted, and the results were satisfactory and without any problems.
実施例８
上記材料をブレンダーでよく混合した後、１４０℃に設
定した２軸混練押出機にて混練した。得られた混練物を
冷却し、カッターミルにて粗粉砕した後、ジェット気流
を用いた微粉砕機を用いて微粉砕し、得られた微粉砕粉
を固定壁型風力分級機で分級した。Example 8 The above materials were thoroughly mixed in a blender, and then kneaded in a twin-screw kneading extruder set at 140°C. The obtained kneaded product was cooled and coarsely pulverized using a cutter mill, then finely pulverized using a pulverizer using a jet stream, and the obtained pulverized powder was classified using a fixed wall type wind classifier.
さらに、得られた分級粉をコアンダ効果を利用した多分
割分級装置（８鉄鉱業社製エルボジェット分級機）で超
微粉を同時に厳密に分級除去して体積平均粒径１１．８
μｍの微粉体を得た。Furthermore, the obtained classified powder was strictly classified and removed at the same time using a multi-division classifier (elbow jet classifier manufactured by 8 Iron Mining Co., Ltd.) that utilized the Coanda effect to achieve a volume average particle size of 11.8.
A fine powder of μm size was obtained.
得られた微粉体１００部にジメチルジクロロシランで疎
水化処理されたシリカ微粉末（ＢＥＴ比表面積２００
ｒｄ／ｇ） ０．４部を加え、ヘンシェルミキサーで混
合してトナーとした。100 parts of the obtained fine powder was added with silica fine powder hydrophobized with dimethyldichlorosilane (BET specific surface area 200
rd/g) was added and mixed using a Henschel mixer to prepare a toner.
次いで平均粒径６５μｍのアクリルコートフェライトキ
ャリア１００部に対して得られたトナー１０部を混合し
て現像剤とした。Next, 10 parts of the obtained toner were mixed with 100 parts of an acrylic coated ferrite carrier having an average particle diameter of 65 μm to prepare a developer.
この現像剤を市販の複写機（商品名ＮＰ−６６５０゜キ
ャノン（株）製）に適用して２３℃７６０％の環境条件
下、複写試験をしたところ、１．３１の良好な画質の画
像が得られた。上記現像剤を用いて、３０００枚連続複
写して耐久性能を調べたところ、初期の画像と比較して
遜色のない良好な画像が得られた。When this developer was applied to a commercially available copying machine (product name NP-6650° manufactured by Canon Co., Ltd.) and a copying test was conducted under an environmental condition of 23°C and 760%, an image with a good image quality of 1.31 was obtained. Obtained. Using the above developer, 3,000 sheets were continuously copied and the durability was examined. As a result, good images comparable to the initial images were obtained.
次いで、１５°Ｃ／１０％、３５℃７８３％の環境条件
下、複写試験をしたところ、同様に良好な結果が得られ
た。Next, when a copying test was conducted under the environmental conditions of 15°C/10% and 35°C/783%, similarly good results were obtained.
実施例９
上記材料をブレンダーでよく混合した後、１５０℃に設
定した２軸混練押出機にて混練した。得られた混練物を
冷却し、カッターミルにて粗粉砕した後、ジェット気流
を用いた微粉砕機を用いて微粉砕し、得られた微粉砕粉
を固定壁型風力分級機で分級した。Example 9 The above materials were thoroughly mixed in a blender, and then kneaded in a twin-screw kneading extruder set at 150°C. The obtained kneaded product was cooled and coarsely pulverized using a cutter mill, then finely pulverized using a pulverizer using a jet stream, and the obtained pulverized powder was classified using a fixed wall type wind classifier.
さらに、得られた分級粉をコアンダ効果を利用した多分
割分級装置（８鉄鉱業社製エルボジェット分級機）で超
微粉を同時に厳密に分級除去して体積平均粒径８．５μ
ｍの微粉体を得た。Furthermore, the obtained classified powder was strictly classified and removed at the same time using a multi-division classifier (elbow jet classifier manufactured by 8 Iron Mining Co., Ltd.) that utilized the Coanda effect, and the volume average particle size was 8.5μ.
A fine powder of m was obtained.
得られた微粉体１００部にヘキサメチルジシラザンで疎
水化処理されたシリカ微粉末（ＢＥＴ比表面積３００
ｒｒｆ／ｇ）０．６部を加え、ヘンシエルミキサーデン
昆合してトナーとした。100 parts of the obtained fine powder was added with silica fine powder hydrophobized with hexamethyldisilazane (BET specific surface area 300).
rrf/g) was added and mixed in a Henschel mixer to obtain a toner.
次いで平均粒径６５μｍのアクリルコートフェライトキ
ャリア１００部に対して得られたトナー５．５部を混合
して現像剤とした。Next, 5.5 parts of the obtained toner was mixed with 100 parts of an acrylic coated ferrite carrier having an average particle size of 65 μm to prepare a developer.
この現像剤を市販のカラー電子写真複写機ＣＬＣｌ（キ
ャノン（株）製）で複写テストした。This developer was subjected to a copying test using a commercially available color electrophotographic copying machine CLCl (manufactured by Canon Inc.).
その結果、２３°Ｃ／６０％の環境条件下で、初期から
画像濃度１．４０の鮮やかな黒色画像が得られ、１万枚
複写後の劣化は認められなかった。As a result, under environmental conditions of 23° C./60%, a bright black image with an image density of 1.40 was obtained from the initial stage, and no deterioration was observed after 10,000 copies were made.
次に、１５℃／１０％の環境条件下で複写試験したとこ
ろ、初期から！、３５の高濃度の画像が得られた。Next, we conducted a copying test under environmental conditions of 15°C/10% and found that from the beginning! , 35 high density images were obtained.
更に、３２℃／８５％の環境条件下においても、濃度１
．４１の良好な画像が得られた。Furthermore, even under the environmental conditions of 32°C/85%, the concentration of
．． 41 good images were obtained.
実施例１０
上記材料をブレンダーでよく混合した後、１５０℃に設
定した２軸混練押出機にて混練した。得られた混練物を
冷却し、カッターミルにて粗粉砕した後、ジェット気流
を用いた微粉砕機を用いて微粉砕し、得られた微粉砕粉
を固定壁型風力分級機で分級した。Example 10 The above materials were thoroughly mixed in a blender, and then kneaded in a twin-screw kneading extruder set at 150°C. The obtained kneaded product was cooled and coarsely pulverized using a cutter mill, then finely pulverized using a pulverizer using a jet stream, and the obtained pulverized powder was classified using a fixed wall type wind classifier.
さらに、得られた分級粉をコアンダ効果を利用した多分
割分級装置（８鉄鉱業社製エルボジェット分級機）で超
微粉を同時に厳密に分級除去して体積平均粒径１１．８
μｍの微粉体を得た。Furthermore, the obtained classified powder was strictly classified and removed at the same time using a multi-division classifier (elbow jet classifier manufactured by 8 Iron Mining Co., Ltd.) that utilized the Coanda effect to achieve a volume average particle size of 11.8.
A fine powder of μm size was obtained.
この微粉体１００部に対し、化合物例（５） １．０部
、シリカ微粉末０．４部をヘンシェルミキサーで混合し
、前処理を行なった。To 100 parts of this fine powder, 1.0 part of Compound Example (5) and 0.4 part of fine silica powder were mixed in a Henschel mixer for pretreatment.
次に第１図の装置を用いて最短間隙１ｍｍ、ブレードの
周速６０ｍ／ｓｅｃ、処理時間５分間の条件にて処理し
た。処理物を電子顕微鏡で観察したところ、トナー表面
に部分的に固着、埋設されているのが観察された。また
、固着率を測定したところ９０％であった。さらにこの
処理物１００部にヘキサメチルジシラザンにより疎水化
処理したシリカ微粉末（ＢＥＴ比表面積３００ポ／ｇ）
０．６部を添加しトナーを得た。Next, processing was performed using the apparatus shown in FIG. 1 under the conditions of a minimum gap of 1 mm, a blade circumferential speed of 60 m/sec, and a processing time of 5 minutes. When the treated product was observed under an electron microscope, it was observed that the toner was partially adhered to and embedded in the surface of the toner. Furthermore, the adhesion rate was measured and found to be 90%. Further, 100 parts of this treated product was treated with silica fine powder (BET specific surface area 300 po/g) that was hydrophobized with hexamethyldisilazane.
A toner was obtained by adding 0.6 part.
このトナーを市販の複写機（商品名Ｎ Ｐ ６６５０
。This toner is used in a commercially available copier (product name: NP 6650).
.
キャノン（株）製）に適用して２３℃／６０％の環境条
件下、複写試験をしたところ、画像濃度１．３１、カブ
リやがさつきのない鮮明な画像が得られた。さらに、１
万枚連続複写して耐久性能を調べたところ、画像濃度１
，３０と初期の画像と比較して遜色のない良好な画像が
得られた。When a copying test was carried out under environmental conditions of 23° C./60% using Canon Co., Ltd., a clear image with an image density of 1.31 and no fogging or roughness was obtained. Furthermore, 1
When we investigated the durability performance by continuously copying 10,000 copies, we found that the image density was 1.
, 30, a good image comparable to the initial image was obtained.
次いで、１５°Ｃ／】０％の環境条件下、複写試験をし
たところ、同様に高濃度で良好な画質の画像が得られた
。１万枚の連続複写試験においても同様に良好な成績で
あった。Next, a copying test was carried out under an environmental condition of 15°C/]0%, and similarly high density and good quality images were obtained. Similarly, good results were obtained in a continuous copying test of 10,000 sheets.
さらに、３５°Ｃ／８５％の環境条件下、同じ複写試験
、連続複写試験を行なったところ、良好な結果であった
。Furthermore, when the same copying test and continuous copying test were conducted under environmental conditions of 35°C/85%, good results were obtained.
実施例１１
イオン交換水１．２００ ｍ ｌにγ−アミノプロピル
トリメトキシシランＯ：５ｇを加え、更にアエロジル２
００（日本アエロジル）ｌｏｇを加え、７０ ’（：に
加温し、Ｔ、に、式ホモミキサーＭ型（特殊機化工業製
）を用いて１１００００ｒｐで１５分間分散させた。さ
らにＮ／ｌ０ＨＣＩ！１９ｇを加え、系内ｐＨを６とし
た。Example 11 5 g of γ-aminopropyltrimethoxysilane O was added to 1.200 ml of ion-exchanged water, and Aerosil 2
00 (Nippon Aerosil) log was added, heated to 70' (T), and dispersed for 15 minutes at 110,000 rpm using a homomixer M type (manufactured by Tokushu Kika Kogyo). Furthermore, N/l0 HCI! 19 g was added to adjust the system pH to 6.
上記処方の成分を容器中で７０℃に加温し、Ｔ 、 Ｋ
。The ingredients of the above formulation were heated to 70°C in a container, and T, K
.
式ホモミキサーＭ型を用いて１１００００ｒｐで５分間
溶解・分散して単量体混合物とした。さらに７０℃に保
持しながら、開始剤Ｖ−６０１（和光紬薬製〉１０部を
加えて溶解し、単量体組成物を調製した。The mixture was dissolved and dispersed using a homomixer M type at 110,000 rpm for 5 minutes to obtain a monomer mixture. Further, while maintaining the temperature at 70°C, 10 parts of initiator V-601 (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) was added and dissolved to prepare a monomer composition.
前記で得た分散媒を入れた２１のフラスコ中に、上記単
量体組成物を投入し、窒素雰囲気下、７０℃でＴ、に、
式ホモミキサーを用いて１１００００ｒｐで６０分間撹
拌し、単量体組成物を造粒した。その後、バドル撹拌翼
で撹拌しつつ、７０ ’Ｃで１０時間重合した。重合反
応終了後、反応生成物を冷却し、ＮａＯＨを加え、分散
剤を溶解し、濾過・水洗・乾燥を行ない、重合トナーを
得た。得られたトナーの粒径は８．５μｍであった。The above monomer composition was put into a No. 21 flask containing the dispersion medium obtained above, and heated to T at 70°C under a nitrogen atmosphere.
The monomer composition was granulated by stirring at 110,000 rpm for 60 minutes using a homomixer. Thereafter, polymerization was carried out at 70'C for 10 hours while stirring with a paddle stirring blade. After the polymerization reaction was completed, the reaction product was cooled, NaOH was added to dissolve the dispersant, and the mixture was filtered, washed with water, and dried to obtain a polymerized toner. The particle size of the obtained toner was 8.5 μm.
このトナーを市販の複写機（商品名ＮＰ−６６５０゜キ
ャノン（株）製）に適用して２３°Ｃ／６０％の環境条
件下、複写試験をしたところ、画像濃度１．３２、カブ
リやがさつきのない鮮明な画像が得られた。さらに、５
０００枚連続複写して耐久性能を調べたところ、画像濃
度１．３０と初期の画像と比較して遜色のない良好な画
像が得られた。When this toner was applied to a commercially available copying machine (product name NP-6650° manufactured by Canon Co., Ltd.) and subjected to a copying test under environmental conditions of 23°C/60%, the image density was 1.32, and fog and fog were observed. Clear images with no scratches were obtained. Furthermore, 5
When the durability performance was examined by continuously copying 000 sheets, a good image with an image density of 1.30, which was comparable to the initial image, was obtained.
次いで、１５°Ｃ７１０％、３５℃／８５％の環境条件
下、複写試験をしたところ、同様に高濃度で良好な画質
の画像が得られた。５０００枚の連続複写試験において
も同様に良好な成績であった。Next, when a copying test was conducted under environmental conditions of 15°C/710% and 35°C/85%, similarly high density and good quality images were obtained. Similarly, good results were obtained in a continuous copying test of 5,000 sheets.
上述したように電荷制御剤として本発明のｐ−フェニル
フェノール−アルデヒド縮合物類ヲ含有するトナーは、
十分な摩擦帯電量を有するとともにトナー粒子間の摩擦
帯電量が均一であり、カブリのない良好な画像を与える
。また電荷制御剤によるスリーブ、キャリア等のトナー
担持体の汚染が減少したために、大量に複写した後も、
十分な濃度の画像が得られ、濃度が安定している。さら
に、温湿度に対する画像濃度の依存性がすくないため広
範囲な環境条件下において優れた品質の画像を提供する
。また、経時変化も起りにくいために、保存中の品質安
定性に優れる。また、加熱混練時に分解変質しないので
、トナー製造時に生じる廃トナーを再利用でき、省資源
化を計れる。As mentioned above, the toner containing the p-phenylphenol-aldehyde condensate of the present invention as a charge control agent includes:
It has a sufficient amount of triboelectric charge, and the amount of triboelectricity between toner particles is uniform, giving a good image without fogging. In addition, since contamination of toner carriers such as sleeves and carriers by charge control agents has been reduced, even after making large quantities of copies,
An image with sufficient density is obtained and the density is stable. Furthermore, since image density is less dependent on temperature and humidity, it provides images of excellent quality under a wide range of environmental conditions. Furthermore, since it is less likely to change over time, it has excellent quality stability during storage. In addition, since it does not decompose or change in quality during heating and kneading, waste toner generated during toner production can be reused, resulting in resource conservation.
さらに、電荷制御剤による色調障害が少ないので、カラ
ートナーに使用することができる。Furthermore, it can be used in color toners because there is little color tone disturbance caused by the charge control agent.
第１図は粒子（Ａ）に粒子（Ｂ）を固着、埋設するため
の装置の一例を概略的に示した説明図である。
１・・・回転軸
２・・・ロータ
４・・・回転片（プレー
５・・・仕切円板
６・・・ケーシング
７・・・ライナー
８・・・衝撃部
９・・・入口室
ＩＯ・・・出口室
１１・・・リターン路
１２・・・製品取出部
１３・・・原材料投入弁
１４・・・ブロワ−
１５・・・ジャケット
ド）
３・・・分散羽根FIG. 1 is an explanatory diagram schematically showing an example of an apparatus for fixing and embedding particles (B) on particles (A). 1... Rotating shaft 2... Rotor 4... Rotating piece (play 5... Partition disk 6... Casing 7... Liner 8... Impact part 9... Inlet chamber IO. ... Outlet chamber 11 ... Return path 12 ... Product take-out section 13 ... Raw material input valve 14 ... Blower 15 ... Jacketed) 3 ... Dispersion vane
Claims (1)
びＲ＿３は、それぞれ独立に、水素、炭素数１乃至６の
アルキル基、ハロゲン、カルボキシル基、ヒドロキシ基
、シアノ基、ニトロ基、ハロゲン化メチル基、トリメチ
ルシリル基、炭素数１乃至８のエステル基、炭素数１乃
至８のアミド基、炭素数１乃至１２のアシル基、炭素数
１乃至８のスルホニル基、または炭素数１乃至８のエー
テル基を示す。） で示される部分構造式を有し、テトラヒドロフランに不
溶なｐ−フェニルフェノール−アルデヒド縮合物類を少
なくとも一種類含有することを特徴とする静電荷像現像
用トナー[Claims] The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents hydrogen or a methyl group, and R_2 and R_3 each independently represent hydrogen or a carbon number of 1 Alkyl group with 1 to 6 carbon atoms, halogen, carboxyl group, hydroxy group, cyano group, nitro group, halogenated methyl group, trimethylsilyl group, ester group with 1 to 8 carbon atoms, amide group with 1 to 8 carbon atoms, 1 to 8 carbon atoms 12 acyl group, a sulfonyl group having 1 to 8 carbon atoms, or an ether group having 1 to 8 carbon atoms. A toner for developing electrostatic images characterized by containing at least one type of
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2034454A JP2851895B2 (en) | 1990-02-14 | 1990-02-14 | Toner for developing electrostatic images |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2034454A JP2851895B2 (en) | 1990-02-14 | 1990-02-14 | Toner for developing electrostatic images |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03237467A true JPH03237467A (en) | 1991-10-23 |
| JP2851895B2 JP2851895B2 (en) | 1999-01-27 |
Family
ID=12414695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2034454A Expired - Fee Related JP2851895B2 (en) | 1990-02-14 | 1990-02-14 | Toner for developing electrostatic images |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2851895B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679489A (en) * | 1993-11-01 | 1997-10-21 | Hodogaya Chemical Co., Ltd. | Electrostatic image developing toner |
| JPH10228134A (en) * | 1997-02-14 | 1998-08-25 | Canon Inc | Toner for developing electrostatic charge image |
| US6534231B1 (en) | 1998-09-22 | 2003-03-18 | Orient Chemical Industries, Ltd. | Charge control agent and toner for developing electrostatic images |
| WO2012118024A1 (en) * | 2011-02-28 | 2012-09-07 | オリヱント化学工業株式会社 | Toner for electrostatic image development |
| WO2012118025A1 (en) * | 2011-02-28 | 2012-09-07 | オリヱント化学工業株式会社 | Charge control agent and toner for electrostatic image development containing same |
| WO2012117952A1 (en) * | 2011-02-28 | 2012-09-07 | Ricoh Company, Ltd. | Toner, and full-color image forming method and full-color image forming apparatus using the toner |
-
1990
- 1990-02-14 JP JP2034454A patent/JP2851895B2/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679489A (en) * | 1993-11-01 | 1997-10-21 | Hodogaya Chemical Co., Ltd. | Electrostatic image developing toner |
| JPH10228134A (en) * | 1997-02-14 | 1998-08-25 | Canon Inc | Toner for developing electrostatic charge image |
| US6534231B1 (en) | 1998-09-22 | 2003-03-18 | Orient Chemical Industries, Ltd. | Charge control agent and toner for developing electrostatic images |
| WO2012118024A1 (en) * | 2011-02-28 | 2012-09-07 | オリヱント化学工業株式会社 | Toner for electrostatic image development |
| WO2012118025A1 (en) * | 2011-02-28 | 2012-09-07 | オリヱント化学工業株式会社 | Charge control agent and toner for electrostatic image development containing same |
| WO2012117952A1 (en) * | 2011-02-28 | 2012-09-07 | Ricoh Company, Ltd. | Toner, and full-color image forming method and full-color image forming apparatus using the toner |
| JP2012177827A (en) * | 2011-02-28 | 2012-09-13 | Ricoh Co Ltd | Toner, method for forming full-color image and full-color image forming apparatus using the toner |
| JP5334277B2 (en) * | 2011-02-28 | 2013-11-06 | オリヱント化学工業株式会社 | Charge control agent and toner for developing electrostatic image containing the same |
| CN103403625A (en) * | 2011-02-28 | 2013-11-20 | 东方化学工业株式会社 | Charge control agent and toner for electrostatic image development containing same |
| CN103492954A (en) * | 2011-02-28 | 2014-01-01 | 株式会社理光 | Toner, and full-color image forming method and full-color image forming apparatus using the toner |
| JP5477831B2 (en) * | 2011-02-28 | 2014-04-23 | オリヱント化学工業株式会社 | Toner for electrostatic image development |
| RU2559452C2 (en) * | 2011-02-28 | 2015-08-10 | Рикох Компани, Лтд. | Toner, method of formation of full-colour images and device for formation of full-colour images, using such toner |
| US9122182B2 (en) | 2011-02-28 | 2015-09-01 | Orient Chemical Industries Co., Ltd. | Charge control agent and toner for electrostatic image development containing same |
| US9152069B2 (en) | 2011-02-28 | 2015-10-06 | Ricoh Company, Ltd. | Toner, and full-color image forming method and full-color image forming apparatus using the toner |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2851895B2 (en) | 1999-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2694572B2 (en) | Toner for developing electrostatic images | |
| JPH03174164A (en) | Production of toner for developing electrostatic charge image | |
| JP2899038B2 (en) | Toner for developing electrostatic images | |
| JPH0692357B2 (en) | Toner for developing electrostatic image containing guanidine compound and guanidine compound | |
| JP2851895B2 (en) | Toner for developing electrostatic images | |
| JP2726745B2 (en) | Toner for developing electrostatic images | |
| JPH0534985A (en) | Electrostatic charge image developing developer, image forming device, device unit, and facsimile device | |
| JP3091921B2 (en) | Toner for developing electrostatic images | |
| JP2748164B2 (en) | Negatively chargeable toner for developing electrostatic latent images | |
| JP2704765B2 (en) | Toner for developing electrostatic images | |
| JP2749998B2 (en) | Two-component developer for negatively charged electrostatic image development | |
| JPH043076A (en) | Electrostatic charge image developing toner | |
| JPH0443366A (en) | Electrostatic image developing toner | |
| JP2726740B2 (en) | Toner for developing electrostatic images | |
| JP2694543B2 (en) | Toner for developing electrostatic images | |
| JPH04343365A (en) | Toner for developing electrostatic charge image | |
| JPH04139461A (en) | Electrostatic charge developing toner | |
| JPH04139457A (en) | Electrostatic charge image developing toner | |
| JP2805355B2 (en) | Negatively charged electrostatic image developing toner | |
| JP2704764B2 (en) | Magnetic toner for developing electrostatic images | |
| JPH06230611A (en) | Electrostatic charge image developing toner | |
| JPH02238465A (en) | Electrostatic charge image developing toner | |
| JP2704027B2 (en) | Negative triboelectric toner for electrostatic image development | |
| JPH02230163A (en) | Dimerized matter of salicylic acid and derivative thereof and toner for developing electrostatic charge image containing this matter | |
| JPH01279258A (en) | Toner for developing electrostatic charge image |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081113 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081113 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091113 Year of fee payment: 11 |
|
| LAPS | Cancellation because of no payment of annual fees |